This review covers applications of ion-molecule reactions for solving
increasingly complex analytical problems. Because gas phase reactions
are frequently fast and efficient, the use of ion-molecule reactions p
rovides a diverse frontier for extending the boundaries of mass spectr
ometry. Product distributions from ion-molecule reactions may provide
key diagnostic information for structure identification, and particula
r product ions may afford more structurally informative fragmentation
patterns than those patterns of ions that are generated by conventiona
l methods. Applications range from those areas involving tile developm
ent of novel chemical ionization reagents that show structural specifi
city upon reactions with analytes, to those areas in which ion-molecul
e reactions are combined with collisionally activated dissociation in
unusual sequences, to those areas involving ion-molecule reactions of
species formed by laser desorption or electrospray ionization. In elec
trospray ionization applications, the use of ion-molecule reactions al
lows the concentration of ion cui-rent into fewer multicharged ions, p
erm its the counting of acidic or basic sites, and provides indirect i
nformation about protein structures and thermochemical data about indi
vidual sites in large molecules. (C) 1997 John Wiley & Sons, Inc.